Lab 2: Calorimetry

1 Objective
The goal of this lab session is to determine the reaction heat for acid-base reactions. The essential reaction
equation for strong acid-base reactions is always the same. So, it is not important which strong acid or
base is used. In this experiment we work with sodium hydroxide (NaOH) with an unkown concentration
and hydrochloric acid (HCl) of exactly 2.00 M. To be able to determine the reaction heat for every mole
of water that was formed, we need to know the exact amount of the limiting reagent. Therefore, it will be
necessary to first determine the limiting reagent, based on titration results with which the concentration
of the NaOH solution is determined. During the practical part of the lab, the reaction heat released by
this acid-base reaction will be determined.

2 Standardization of the NaOH solution

2.1 Theory
2.1.1 Standardization
The concentration of the NaOH solution used, must be known accurately to be able to obtain exact results
afterwards. However, some of the commonly used solutions are difficult to prepare in such a way that
their concentration is precisely known. For example, the concentration of a solution of NaOH, which
is prepared by weighing a known amount of solid NaOH, is never known exactly because during the
weighing, NaOH reacts with CO2 and water, present in the air.
The concentration must therefore be checked after preparation. This can be done using a solution
whose concentration can be accurately known. This procedure is called standardization. The solution that
is used for standardization is called the primary standard. For example, a NaOH solution is standardized
with a solution of oxalic acid (C2 H2 O4 ), a diprotic acid.

2.1.2 Principle of titration

Titration is a method for determining the concentration of a solution or a quantity of a compound by
using a reaction with another solution of an accurately known concentration. The equivalence point (or
stoichiometric point) corresponds to the moment when the compound to be analyzed has completely
reacted and no excess of the compound is added.
By determining the equivalence point one can calculate the amount of compound to be analyzed if:
• the concentration of the other compound is known,
• the chemical reaction between both reactants is known,
• the reaction is executed completely.
How the equivalence point is determined, depends on the kind of reaction. Different methods to
determine the equivalence point will be used for acid-base reactions, redox reactions, precipitation reac-
tions and others. In acid-base titrations, the concentration of an acidic (or basic) solution is determined
by using a reaction with a base (or acid) with a known concentration. The moment at which an equival-
ent amount of acid and base is present can be visualized by means of an acid-base indicator (eg methyl
orange or phenolphthalein).

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Question 1. What is an acid-base indicator?

Question 2. Search for the color changes and transition points for phenolphthalein and methyl orange.

Question 3. When should phenolphthalein be used and when methyl orange? Explain.

2.1.3 Detailed example

If the concentration of an HCl solution is to be determined, a solution of a base (here: NaOH) with a
known concentration (here: 0.1 M) is slowly added to a known volume of the acid solution (here: 5 ml
diluted to 25 ml). Phenolphthalein is used as indicator in this example. The following reaction occurs:

NaOH + HCl ! NaCl + H2 O

The essential reaction equation is:

OH + H+ ! H2 O
The reaction equation shows that all HCl will be consumed as soon as an equivalent amount of NaOH will
be added. In the table below you can find an overview of the important parameters and the experimental
results (VNaOH, added ) for this titration.

Example acid-base titration

Acid HCl (unknown concentration)
Base NaOH (exactly 0.1M)
Titration reaction NaOH + HCl ! NaCl + H2 O
Dilution factor prior to titration 5 (because 5 ml was diluted to 25 ml)
VHCl solution 25.0 ml
VNaOH,added Titration 1: 18.4 ml
Titration 2: 18.3 ml
Titration 3: 18.5 ml
Average: 18.4 · 10 3 l

Since, according to the reaction equation, 1 mole of titrant (NaOH) reacts with 1 mole of the solution
to be titrated (HCl), the number of moles of HCl can be determined by calculating the number of moles
of NaOH.

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nNaOH = cNaOH ·VNaOH = 0.1 M · 18.4 · 10 l = 0.00184 mol = nin 25 ml diluted HCl
Therefore, the concentration of the diluted HCl solution is:
nin 25 ml diluted HCl 0.00184 mol
cdiluted HCl = = = 0.0736 M
Vdiluted HCl 25 · 10 3 l
When taking into account the dilution factor, the concentration of the undiluted solution can be calcu-
lated:
cundiluted HCl = cdiluted HCl · dilution factor = 0.0736 M · 5 = 0.368 M

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2.2 Determination of the concentration of NaOH
2.2.1 Method
Due to time constraints, this experiment is not performed. Use the method below and the results given to
calculate the concentration of NaOH.

1. From the NaOH solution whose concentration is to be determined, a new solution with a dilution
factor of 10 is made in a 100 ml volumetric flask
2. Using a beaker, stirrer and a 100 ml volumetric flask, an (approximately) 0.1 M oxalic acid
(HOOCCOOH · 2 H2 O) solution is made. Although the concentration does not have to be exactly
0.1 M, the weighed mass must be known exactly to calculate the exact concentration
3. Exactly 20 ml of this oxalic acid solution is pipetted into an erlenmeyer flask using a volumetric
pipette. Also a few drops of indicator (phenolphthalein) are added
4. Three titrations are performed to the equivalence point with a maximum difference in volume of
0.5 ml

Question 4. Write the molecular equation of this chemical reaction. Note: oxalic acid is a diprotic acid.

Question 5. How much oxalic acid dihydrate HOOCCOOH · 2 H2 O should you weigh in order to obtain
a 0.1 M solution? Take into account the two water molecules that are present for every oxalic acid
molecule.

2.2.2 Results

Mass of oxalic acid 1.35 g

Titration 1: Volume of NaOH added 17.8 ml

Titration 2: Volume of NaOH added 18.1 ml

Titration 3: Volume of NaOH added 17.7 ml

Question 6. Calculate the concentration of the (undiluted) sodium hydroxide solution on the basis of the
reaction equation, method and results above.

Concentration of oxalic acid solution

Average Volume of NaOH added

Concentration of diluted NaOH solution

Concentration of undiluted NaOH solution

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Question 7. In the practical test we work with a HCl solution of exactly 2.00 M (4.00 M with a dilution
factor of 2) and with the (undiluted) NaOH solution of which you just determined the concentration.
Which reagent will be limiting?

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3 Determination of the heat of the reaction
3.1 Theory
3.1.1 General
When a reaction is carried out under constant pressure, the heat change is equal to the change in enthalpy.
This change in enthalpy, called the enthalpy of the reaction, can be positive or negative. For endothermic
processes DH is positive, for exothermic processes DH is negative. This change in enthalpy can be
written together with the reaction equation with indication of the aggregation states of both reagents and
reaction product, giving rise to the so-called thermochemical equation, eg

CH4(g) + 2 O2(g) ! CO2(g) + 2 H2 O(l) DH = 890.4 kJ/mol

In the laboratory, heat changes of chemical reaction are measured with a calorimeter. In the exper-
iment described below, a closed container is used, representing a simple constant-pressure calorimeter.
The temperature change measured in the calorimeter is a measure for the enthalpy.

3.1.2 Determination of the heat capacity of the calorimeter

When a reaction is carried out in a calorimeter, part of the heat released during the reaction will be
absorbed by the calorimeter itself. This absorbed heat will not be measured as a temperature change
and introduces an error in the measurements. Therefore, the calorimeter constant Ccalorimeter , the heat
capacity of the calorimeter, should be determined for the calorimeter used.

Question 8. What is heat capacity (C)? What is specific heat (s)? Find the specific heat for water as a
fluid. is a physical property of matter, defined as the amount of heat to be
supplied to an object to produce a unit change in its temperature.

To determine this calorimeter constant, we use the principle of conservation of energy. A known
quantity of water is introduced in the calorimeter. When the thermic equilibrium is reached, meaning the
temperature remains stable, a known quantity of hot water is added. The heat released by the hot water
is absorbed by the cold water and the calorimeter. Using the equation below, the heat capacity of the
calorimeter can be determined.

Question 9. Prove that the following equation describes the heat change. Start with qsys = 0

[(msDT )cold water + (msDT )hot water ]

Ccalorimeter = with DT = Tend Tstart
DTcalorimeter
Question 10. Do you expect a negative or positive value for Ccalorimeter ? Explain.

3.1.3 Determination of the heat of the reaction

A known volume of the first reagent is brought in the calorimeter. The second solution is poured in
a separate beaker. The temperature of both solutions is measured. When both solutions have reached
the same temperature, they are mixed in the calorimeter while monitoring the temperature. During this
experiment the reaction heat of acid-base reactions is measured.

3.2 Materials
• Glassware
– Beaker 250 ml
– Volumetric pipette 20 ml, 25 ml and 50 ml
– Volumetric flask 250 ml
• Calorimeter: insulating mug

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 • Digital thermometer
• Stirring rod
• Hot plate
• Solutions
– 4 M HCl solution
– NaOH solution with a concentration determined in question 6

Question 11. Explain how one can (theoretically) make a 4 M HCl solution from a concentrated solution
of HCl with concentration of 37% and a density of 1.18 kg/l.

3.3 Method
3.3.1 Determination of the heat capacity of the calorimeter
1. Make sure the calorimeter is dry before use. Through the hole in the lid, you can stir and measure
the temperature. Because the density of water is almost 1.00 g/ml over a wide temperature range,
the mass of the water will be determined using the volume
2. Transfer exactly 70.0ml cold water in the calorimeter. Close the lid and apply the thermometer
and stirring rod
3. Pour the same volume of water in a dry beaker and heat to 70–80°C. Mix occasionally while
heating to make sure the solution has a homogenous temperature. Simultaneously, monitor the
temperature of the cold water for 2-3 minutes to make sure it is constant. Record the temperature
as accurately as possible
4. Remove the beaker from the hot plate when 70-80°C is reached. Stir occasionally when the beaker
is left alone for 2-3 minutes. Record the temperature as accurately as possible
5. Remove the lid of the calorimeter and pour the hot water quickly into the cold water. Immediately
place the lid back on and stir for 30 seconds. Follow the temperature of the water in the calorimeter
and record the highest value as accurately as possible

Execute the experiment at least 2 times. Use the average value of your measurements for the calcu-
lation of the calorimeter constant. Dry the calorimeter before retaking the experiment.

3.3.2 Determination of the heat of the reaction

1. Make 250 ml of a dilution with dilution factor 2 of the available HCl solution
2. Transfer exactly 70 ml NaOH in the dry calorimeter. Transfer exactly 70 ml of the 2 M HCl
solution in a dry beaker. Wait until the solutions have the same temperature (if this takes too long,
take the average of both temperatures as start temperature). Record the temperature as accurately
as possible
3. Pour the acidic solution at once in the calorimeter. Quickly close the calorimeter. Stir for 30
seconds and record the highest temperature that was reached as accurately as possible

Execute the experiment at least 2 times. From the temperature change of the mixture, the total
volume (total mass) of the 2 solutions and the calorimeter constant of the apparatus, the reaction heat
that is transferred from the reacting particles to the water can be calculated. Assume that the density and
the specific heat of the solution in the calorimeter is the same as for pure water.

Question 12. Write the essential equation for this specific experiment.

Question 13. How many moles of H2 O is formed in this experiment if a HCl solution of exactly 2 M
and a NaOH solution with the molarity as calculated in question 6?

Question 14. Calculate by means of standard formation enthalpy values, the enthalpy change of the
neutralization reaction.

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3.4 Results
Do not forget to provide your results with the right units.

3.4.1 Determination of the heat capacity of the calorimeter

Experiment 1 Experiment 2

Mass of cold water

Temperature of cold water

Mass of hot water

Temperature of hot water

Temperature after mixing

Ccalorimeter

Ccalorimeter,average

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3.4.2 Determination of the heat of the reaction
Experiment 1 Experiment 2

Tstart

Tend

DT

Mass of solution

Amount of water formed (mol)

Keep in mind the calculated
concentration of NaOH from
chapter 6

qreaction

qreaction,average

DH(for every mol H2 O formed)

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4 Conclusion

Critically analyze your calcu-

lated value for Ccalorimeter . What
does this mean in practice?

Theoretical value for enthalpy

change of the neutralization re-
action

Experimental value for enthalpy

change of the neutralization re-
action

Compare the experimental with

the theoretical value and discuss

5 H and P phrases
H(azard) phrases describe the risks associated with working with these products, while P(recautionary)
phrases give an idea of the safety regulations.